CN108011090B - Method for preparing lithium ion battery cathode, battery cathode prepared by method and lithium ion battery - Google Patents
Method for preparing lithium ion battery cathode, battery cathode prepared by method and lithium ion battery Download PDFInfo
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Abstract
The invention provides a method for preparing a porous copper silicon lithium ion battery cathode, which comprises the following steps: selecting copper powder and silicon powder with different particle sizes as raw materials; carrying out first oxidation treatment on copper powder; carrying out first reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the pore diameter of pores is between 200 and 500nm, and the porosity is between 20 and 35 percent; carrying out second oxidation treatment on the copper powder; carrying out second reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the pore diameter of pores is between 300 and 600nm, and the porosity is between 25 and 45 percent; mixing the reduced copper powder with silicon powder, and then carrying out ball milling, wherein the mass ratio of the reduced copper powder to the silicon powder is 4:1-1:1, and the ball milling time is controlled to be 10-15 h, so as to obtain alloyed powder; sieving the obtained alloying powder; and then performing a third reduction treatment on the sieved alloying powder. The battery cathode has good cycle performance, and the capacity retention rate is high after multi-cycle circulation.
Description
Technical Field
The invention relates to a preparation method of a lithium ion battery cathode and the lithium ion battery cathode, in particular to a preparation method of a porous copper silicon lithium ion battery cathode and the porous copper silicon lithium ion battery cathode.
Background
The current energy and environmental crisis is increasingly serious, and the development of new energy is increasingly important for solving the harm caused by the rapid consumption of non-renewable energy. The lithium ion battery has the advantages of high energy density, no memory effect, environmental friendliness and the like, and is a new energy storage device. The lithium ion battery generally uses activated carbon and the like as negative electrode materials, because the activated carbon and other carbon material allotropes are low in price, stable in performance and already commercialized, but the theoretical capacity of the carbon material is only 372mAh/g, and the demand of rapidly developing power equipment is difficult to meet. In order to further improve the energy density of the lithium ion battery, the selection and the structural design of the cathode material are crucial. The copper oxide has high theoretical capacity because of low price, and is highly regarded by the research field. However, poor conductivity of copper oxide becomes a serious drawback. In order to solve the problem of conductivity, the conductivity and stability of the copper oxide-based negative electrode are improved by adopting a compounding and coating mode at present. The silicon negative electrode material becomes the research focus of the current enterprises and scientific research institutes because the theoretical capacity is up to 4200mAh/g, but the silicon has poor conductivity and high expansion coefficient, so that the silicon is difficult to be used as the negative electrode material of the commercial lithium ion battery independently, and meanwhile, the expansion/contraction effect of the silicon easily causes pulverization and falling of the material, and finally causes the defects of rapid performance attenuation and short circuit.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a method for preparing a porous copper silicon lithium ion battery cathode, the porous copper silicon lithium ion battery cathode prepared by the method and a lithium ion battery, so that the defects of the prior art are overcome.
In order to achieve the purpose, the invention provides a method for preparing a porous copper silicon lithium ion battery cathode, which is characterized by comprising the following steps: the method comprises the following steps: selecting copper powder and silicon powder with different particle sizes as raw materials; carrying out first oxidation treatment on copper powder; carrying out first reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the pore diameter of pores is between 200 and 500nm, and the porosity is between 20 and 35 percent; carrying out second oxidation treatment on the copper powder; carrying out second reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the pore diameter of pores is between 300 and 600nm, and the porosity is between 25 and 45 percent; mixing the reduced copper powder with silicon powder, and then carrying out ball milling, wherein the mass ratio of the reduced copper powder to the silicon powder is 4:1-1:1, and the ball milling time is controlled to be 10-15 h, so as to obtain alloyed powder; sieving the obtained alloying powder; and then performing a third reduction treatment on the sieved alloying powder.
Preferably, in the above technical scheme, the particle size of the copper powder is 5-10um, and the particle size of the silicon powder is 100-150 nm.
Preferably, in the above technical solution, the first oxidation treatment of the copper powder specifically includes: the copper powder is subjected to oxidation treatment for 2-3h under the conditions of 500-600 ℃.
Preferably, in the above technical solution, the performing the first reduction treatment on the oxidized copper powder specifically includes: the copper powder is subjected to reduction treatment for 2-3h under the conditions of hydrogen atmosphere and temperature of 500-600 ℃.
Preferably, in the above technical solution, the second oxidation treatment of the copper powder specifically includes: the copper powder is subjected to oxidation treatment for 2-3h at the temperature of 550-650 ℃.
Preferably, in the above technical solution, the second reduction treatment of the oxidized copper powder specifically includes: the copper powder is subjected to reduction treatment for 2-3h under the conditions of hydrogen atmosphere and temperature of 550-650 ℃.
Preferably, in the above technical solution, the method further includes: after the third reduction treatment of the alloyed powder, the alloyed powder after the third reduction is subjected to etching using dilute nitric acid.
The invention also provides a porous copper silicon lithium ion battery cathode, which is characterized in that: the porous copper silicon lithium ion battery cathode is prepared by the method.
The invention also provides a lithium ion battery, which is characterized in that: the lithium ion battery comprises a porous copper silicon lithium ion battery cathode, and the porous copper silicon lithium ion battery cathode is prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
in order to solve the defects of the copper oxide and the silicon-based negative electrode. The invention adopts a simple oxidation-reduction process to form a porous structure on the surface of copper particles, ball-milling the obtained porous copper precursor and nano-silicon powder to prepare the porous copper-silicon lithium electric novel composite material, further carrying out secondary corrosion pore-forming by dilute nitric acid and reduction treatment under a hydrogen protective atmosphere on the ball-milled novel composite material, corroding part of copper and reducing copper oxide particles to form a hierarchical pore structure electrode. The advantages are that: 1. the original copper powder is subjected to a twice-oxidation-reduction pore-forming method, wherein a smaller and shallower pore is formed by first oxidation-reduction, and the pore is enlarged and deepened by second oxidation-reduction, so that the subsequent compounding with the silicon powder is facilitated; 2. the copper particles with the porous structure can form a silicon embedded structure in the ball milling process, so that the volume expansion effect is buffered; 3. the porous copper structure has excellent conductivity, so that the electronic conductivity of a silicon-copper interface can be effectively improved, and the electrochemical performance is further improved; 4. the porous copper structure is beneficial to improving the loading capacity of the active silicon and further improving the specific capacity; 5. the selected raw materials have rich mineral products and the preparation method is simple.
Drawings
Fig. 1 is an SEM image of porous copper according to example 1 of the present invention.
Detailed Description
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component. The feedstock of the present invention may be purchased from chemical stores and the heat treatment may be carried out in a conventional heat treatment furnace. Porosity is defined herein as the "ratio of pore area to total surface area".
Example 1
Selecting copper powder and silicon powder with different particle sizes as raw materials; carrying out first oxidation treatment on copper powder; carrying out first reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the pore diameter of pores is 200nm, and the porosity is 20%; carrying out second oxidation treatment on the copper powder; carrying out second reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the pore diameter of pores is 300nm, and the porosity is 25%; mixing the reduced copper powder with silicon powder, and then carrying out ball milling, wherein the mass ratio of the reduced copper powder to the silicon powder is 4:1, and the ball milling time is controlled to be 10 hours, so as to obtain alloyed powder; sieving the obtained alloying powder; and then performing a third reduction treatment on the sieved alloying powder. Preferably, in the above technical scheme, the particle size of the copper powder is 5um, and the particle size of the silicon powder is 100 nm. The first oxidation treatment of the copper powder comprises the following specific steps: the copper powder was subjected to an oxidation treatment at 500 ℃ for 2 hours. The first reduction treatment of the oxidized copper powder comprises the following specific steps: the copper powder is subjected to reduction treatment for 2 hours under the conditions of hydrogen atmosphere and 500 ℃. The second oxidation treatment of the copper powder comprises the following specific steps: the copper powder was subjected to an oxidation treatment at 550 ℃ for 2 hours. The second reduction treatment of the oxidized copper powder comprises the following specific steps: and carrying out reduction treatment on the copper powder for 2h under the conditions of hydrogen atmosphere and 550 ℃. The method further comprises the following steps: after the third reduction treatment of the alloyed powder, the alloyed powder after the third reduction is subjected to etching using dilute nitric acid.
Example 2
Selecting copper powder and silicon powder with different particle sizes as raw materials; carrying out first oxidation treatment on copper powder; carrying out first reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the aperture of a pore is 500nm, and the porosity is 35%; carrying out second oxidation treatment on the copper powder; carrying out second reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the aperture of pores is 600nm, and the porosity is 45%; mixing the reduced copper powder with silicon powder, and then carrying out ball milling, wherein the mass ratio of the reduced copper powder to the silicon powder is 1:1, and the ball milling time is controlled to be 15h, so as to obtain alloyed powder; sieving the obtained alloying powder; and then performing a third reduction treatment on the sieved alloying powder. Preferably, in the above technical solution, the particle size of the copper powder is 10um, and the particle size of the silicon powder is 150 nm. The first oxidation treatment of the copper powder comprises the following specific steps: the copper powder was subjected to oxidation treatment at 600 ℃ for 3 hours. The first reduction treatment of the oxidized copper powder comprises the following specific steps: and carrying out reduction treatment on the copper powder for 3 hours under the conditions of hydrogen atmosphere and 600 ℃. The second oxidation treatment of the copper powder comprises the following specific steps: the copper powder was subjected to oxidation treatment at 650 ℃ for 3 hours. The second reduction treatment of the oxidized copper powder comprises the following specific steps: the copper powder was subjected to reduction treatment for 3 hours in a hydrogen atmosphere at a temperature of 650 ℃. The method further comprises the following steps: after the third reduction treatment of the alloyed powder, the alloyed powder after the third reduction is subjected to etching using dilute nitric acid.
Example 3
Selecting copper powder and silicon powder with different particle sizes as raw materials; carrying out first oxidation treatment on copper powder; carrying out first reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the aperture of a pore is 350nm, and the porosity is 30%; carrying out second oxidation treatment on the copper powder; carrying out second reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the aperture of a pore is 500nm, and the porosity is 40%; mixing the reduced copper powder with silicon powder, and then carrying out ball milling, wherein the mass ratio of the reduced copper powder to the silicon powder is 2:1, and the ball milling time is controlled to be 12h, so that alloyed powder is obtained; sieving the obtained alloying powder; and then performing a third reduction treatment on the sieved alloying powder. Preferably, in the above technical scheme, the particle size of the copper powder is 7um, and the particle size of the silicon powder is 120 nm. The first oxidation treatment of the copper powder comprises the following specific steps: the copper powder was subjected to oxidation treatment at 550 ℃ for 2.5 h. The first reduction treatment of the oxidized copper powder comprises the following specific steps: the copper powder was subjected to reduction treatment for 2.5 hours in a hydrogen atmosphere at a temperature of 550 ℃. The second oxidation treatment of the copper powder comprises the following specific steps: the copper powder was subjected to oxidation treatment at 580 ℃ for 2.5 hours. The second reduction treatment of the oxidized copper powder comprises the following specific steps: the copper powder was subjected to reduction treatment for 2.5 hours in a hydrogen atmosphere at a temperature of 580 ℃. The method further comprises the following steps: after the third reduction treatment of the alloyed powder, the alloyed powder after the third reduction is subjected to etching using dilute nitric acid.
Example 4
Selecting copper powder and silicon powder with different particle sizes as raw materials; carrying out first oxidation treatment on copper powder; carrying out first reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the pore diameter of pores is 300nm, and the porosity is 25%; the second oxidation reduction is not carried out; the first oxidation treatment of the copper powder comprises the following specific steps: the copper powder was subjected to an oxidation treatment at 750 ℃ for 10 hours. The first reduction treatment of the oxidized copper powder comprises the following specific steps: the copper powder was subjected to reduction treatment for 10 hours in a hydrogen atmosphere at a temperature of 700 ℃. The remaining conditions and steps were the same as in parametric example 1.
Example 5
Selecting copper powder and silicon powder with different particle sizes as raw materials; carrying out first oxidation treatment on copper powder; carrying out first reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the pore diameter of pores is 100nm, and the porosity is 15%; carrying out second oxidation treatment on the copper powder; carrying out second reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the pore diameter of pores is 200nm, and the porosity is 20%; the first oxidation treatment of the copper powder comprises the following specific steps: the copper powder was subjected to an oxidation treatment at 500 ℃ for 1 hour. The first reduction treatment of the oxidized copper powder comprises the following specific steps: the copper powder was subjected to reduction treatment for 1 hour in a hydrogen atmosphere at a temperature of 500 ℃. The second oxidation treatment of the copper powder comprises the following specific steps: the copper powder was subjected to an oxidation treatment at 550 ℃ for 1 hour. The second reduction treatment of the oxidized copper powder comprises the following specific steps: the copper powder was subjected to reduction treatment for 1 hour under a hydrogen atmosphere at a temperature of 550 ℃. The remaining conditions and steps were the same as in parametric example 1.
Example 6
Selecting copper powder and silicon powder with different particle sizes as raw materials; carrying out first oxidation treatment on copper powder; carrying out first reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the pore diameter of pores is 100nm, and the porosity is 15%; carrying out second oxidation treatment on the copper powder; carrying out second reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the aperture of a pore is 350nm, and the porosity is 30%; the first oxidation treatment of the copper powder comprises the following specific steps: the copper powder was subjected to an oxidation treatment at 500 ℃ for 1 hour. The first reduction treatment of the oxidized copper powder comprises the following specific steps: the copper powder was subjected to reduction treatment for 1 hour in a hydrogen atmosphere at a temperature of 500 ℃. The second oxidation treatment of the copper powder comprises the following specific steps: the copper powder was subjected to oxidation treatment at 700 ℃ for 3 hours. The second reduction treatment of the oxidized copper powder comprises the following specific steps: the copper powder was subjected to reduction treatment for 3 hours in a hydrogen atmosphere at a temperature of 700 ℃. The remaining conditions and steps were the same as in parametric example 1.
Example 7
Selecting copper powder and silicon powder with different particle sizes as raw materials; carrying out first oxidation treatment on copper powder; carrying out first reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the pore diameter of pores is 200nm, and the porosity is 25%; carrying out second oxidation treatment on the copper powder; carrying out second reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the aperture of a pore is 250nm, and the porosity is 35%; the first oxidation treatment of the copper powder comprises the following specific steps: the copper powder was subjected to an oxidation treatment at 500 ℃ for 2 hours. The first reduction treatment of the oxidized copper powder comprises the following specific steps: the copper powder is subjected to reduction treatment for 2 hours under the conditions of hydrogen atmosphere and 500 ℃. The second oxidation treatment of the copper powder comprises the following specific steps: the copper powder was subjected to oxidation treatment at 550 ℃ for 1.5 h. The second reduction treatment of the oxidized copper powder comprises the following specific steps: the copper powder was subjected to reduction treatment for 1.5 hours in a hydrogen atmosphere at a temperature of 550 ℃. The remaining conditions and steps were the same as in parametric example 1.
Example 8
Selecting copper powder and silicon powder with different particle sizes as raw materials; carrying out first oxidation treatment on copper powder; carrying out first reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the aperture of a pore is 600nm, and the porosity is 40%; carrying out second oxidation treatment on the copper powder; carrying out second reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the aperture of a pore is 800nm, and the porosity is 50%; the first oxidation treatment of the copper powder comprises the following specific steps: the copper powder is subjected to oxidation treatment for 20h at 900 ℃. The first reduction treatment of the oxidized copper powder comprises the following specific steps: and carrying out reduction treatment on the copper powder for 25 hours under the conditions of hydrogen atmosphere and 900 ℃. The second oxidation treatment of the copper powder comprises the following specific steps: the copper powder was subjected to oxidation treatment at 8500 ℃ for 10 hours. The second reduction treatment of the oxidized copper powder comprises the following specific steps: the copper powder is subjected to reduction treatment for 10 hours under the conditions of hydrogen atmosphere and 900 ℃. The remaining conditions and steps were the same as in parametric example 1.
Example 9
The mass ratio of the reduced copper powder to the silicon powder was 5:1, and the other conditions and steps were the same as in parametric example 1.
Example 10
The mass ratio of the reduced copper powder to the silicon powder was 2:1, and the other conditions and steps were the same as in parametric example 1.
Example 11
The ball milling time is controlled to be 5h, and the rest conditions and steps are the same as the parameters in example 1.
Example 12
Sieving the obtained alloying powder; then dilute nitric acid is directly used for corroding the screened alloying powder without carrying out third reduction treatment. The remaining conditions and steps were the same as in parametric example 1.
Example 13
The particle diameter of the copper powder was 4um, and the other conditions and steps were the same as in parameter example 1.
Example 14
The particle diameter of the copper powder was 12um, and the other conditions and steps were the same as in parametric example 1.
Example 15
The particle diameter of the silicon powder is 80nm, and the rest conditions and steps are the same as the parameters in example 1.
Example 16
The particle diameter of the silicon powder is 170nm, and the rest conditions and steps are the same as the parameters in example 1.
Example 17
After the third reduction treatment of the alloyed powder, the etching of the alloyed powder after the third reduction was not performed using the dilute nitric acid, and the remaining conditions and steps were the same as in parametric example 1.
The negative electrode of the battery was assembled using the materials prepared in examples 1 to 17, and the battery capacity was tested by a method known in the art in units of mAh/g. The test contents include first-round capacity, stabilized capacity, 50-round-cycled capacity, and 300-round-cycled capacity. For comparison, the results were normalized to the first-turn capacity of example 1.
TABLE 1
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (3)
1. A method for preparing a porous copper silicon lithium ion battery cathode is characterized by comprising the following steps: the method comprises the following steps: selecting copper powder and silicon powder with different particle sizes as raw materials; carrying out first oxidation treatment on copper powder; carrying out first reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the aperture of a pore is 350nm, and the porosity is 30%; carrying out second oxidation treatment on the copper powder; carrying out second reduction treatment on the oxidized copper powder to reduce the surface of CuO particles so as to form an oxygen vacancy type porous copper structure, wherein the aperture of a pore is 500nm, and the porosity is 40%; mixing the reduced copper powder with silicon powder, and then carrying out ball milling, wherein the mass ratio of the reduced copper powder to the silicon powder is 2:1, and the ball milling time is controlled to be 12h, so that alloyed powder is obtained; sieving the obtained alloying powder; and then carrying out third reduction treatment on the screened alloying powder, wherein the particle size of the copper powder is 7 microns, the particle size of the silicon powder is 120nm, and the first oxidation treatment on the copper powder specifically comprises the following steps: carrying out oxidation treatment on copper powder for 2.5h at 550 ℃, wherein the first reduction treatment on the oxidized copper powder specifically comprises the following steps: under the conditions of hydrogen atmosphere and 550 ℃, the copper powder is subjected to reduction treatment for 2.5h, and the second oxidation treatment of the copper powder specifically comprises the following steps: carrying out oxidation treatment on copper powder for 2.5h at 580 ℃, wherein the second reduction treatment on the oxidized copper powder specifically comprises the following steps: the copper powder is subjected to reduction treatment for 2.5h under the conditions of hydrogen atmosphere and temperature of 580 ℃, and the method further comprises the following steps: after the third reduction treatment of the alloyed powder, the alloyed powder after the third reduction is subjected to etching using dilute nitric acid.
2. A porous copper silicon lithium ion battery cathode is characterized in that: the porous copper silicon lithium ion battery negative electrode is prepared by the method of claim 1.
3. A lithium ion battery, characterized by: the lithium ion battery comprises a porous copper silicon lithium ion battery negative electrode prepared by the method of claim 1.
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"锂离子电池硅铜复合负极材料的研究";左朋建等;《第十三次全国电化学会议》;20051130;第458-459页 * |
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